Lubricating Composition Containing a Dispersant

ABSTRACT

The invention provides a lubricating composition containing a compound comprising the reaction product of a polyolefin, an ethylenically unsaturated aromatic acylating agent (or carboxylic reactant), and an amine, and an oil of lubricating viscosity. The invention further relates to the use of the lubricating composition in an internal combustion engine.

FIELD OF INVENTION

The invention provides a lubricating composition containing a dispersantand an oil of lubricating viscosity. The invention further relates tothe use of the lubricating composition in an internal combustion engine.

BACKGROUND OF THE INVENTION

Engine manufacturers have focused on improving engine design in order tominimise emissions of particulates and pollutants, and improvecleanliness and fuel economy. One of the improvements in engine designis the use of exhaust gas recirculation (EGR) engines. Heavy duty dieselvehicles may use exhaust gas recirculation (EGR) engines in efforts toreduce environmental emissions. Whilst improvements in engine design andoperation have contributed to reducing emissions, some engine designadvances are believed to have generated other challenges for thelubricant. For example, EGR is believed to have led to increasedformation and/or accumulation of soot and sludge. Among the consequencesof recirculating the exhaust gas through the engine are different sootstructures and increased viscosity of the oil at lower soot levels,compared with engines without EGR.

Increased soot-mediated oil thickening is common in heavy duty dieselengines. Some diesel engines employ EGR. The soot formed in an EGRengine has different structures and causes increased viscosity of enginelubricant at lower soot levels than formation of soot in the enginewithout an EGR.

Viscosity improvers are often used to reduce the extent of the decreasein viscosity as the temperature is raised or to reduce the extent of theincrease in viscosity as the temperature is lowered, or both. Thus, aviscosity improver ameliorates the change of viscosity of an oilcontaining it with changes in temperature.

Dispersant viscosity modifiers (DVMs) made from ethylene-propylenecopolymers that have been radically grafted with maleic anhydride andreacted with various amines have shown desirable performance to preventoil thickening in diesel engines. Aromatic amines are said to show goodperformance in this regard. DVMs of this type are disclosed in, forinstance, U.S. Pat. Nos. 4,863,623, 5,264,139, 5,264,140, 5,620,486,6,107,257, 6,107,258, and 6,117,825.

U.S. Pat. No. 5,409,623 discloses functionalized graft copolymers asviscosity index improvers, comprising an ethylene alpha-monoolefincopolymer grafted with an ethylenically unsaturated carboxylic acidmaterial and derivatized with an azo-containing aromatic amine compound.

U.S. Pat. Nos. 5,264,139 and 5,264,140 disclose polymers derivatizedwith a sulphonyl-containing aromatic amine and an amide-containingaromatic amine material respectively.

Other dispersant viscosity modifiers have been contemplated in a varietyof applications including U.S. patent application Ser. Nos. 11/568,051,and 61/118,012; and International Application WO publication WO2010/014655 A1.

U.S. patent application Ser. No. 11/568,051 discloses soot dispersantsderived from esterified maleic anhydride-styrene interpolymersfunctionalized with nitrogen-containing moieties.

International Application WO publication WO2010014655 A1 discloses alphaolefin maleic anhydride (AOMA) interpolymers which may be esterified andfurther functionalized with amines having at least one condensable N—Hgroup.

U.S. application 61/118,012 (also relating to International PatentApplication WO2010/062842) discloses olefin polymers functionalized bygrafting with an unsaturated carboxylic acid material and derivatizedwith aromatic amines having three or more non-contiguous aromaticgroups.

Other publications disclose the possibility of dispersants with aromaticgroups.

U.S. Pat. No. 5,182,041 discloses polyolefin based dispersantsfunctionalized with an ethylenically unsaturated acylating agent andreacted with an amino-aromatic polyamine to produce antioxidantdispersants.

U.S. Pat. No. 6,051,537 discloses hydrocarbyl dispersants made frompolyolefins functionalized with monounsaturated mono acid materialsselected from acrylic acid, methacrylic acid and cinnamic acid reactedwith amines, alcohols and/or aminoalcohols. These polyolefins havenumber average molecular weight in the range 1500 to 5000.

SUMMARY OF THE INVENTION

An objective of the present invention is to provide a lubricatingcomposition capable of providing at least one of (i) a lubricatingcomposition capable of reducing viscosity increase (often having aviscosity of less than 12 mm²/sec (cSt) at 100° C. at a soot loading of6 weight % or more), and/or (ii) a lubricating oil composition thatmaintains a relatively stable viscosity over a wide range oftemperatures. This could be desirable because viscosity index improversor DVMs may be employed to control viscosity over a wide temperaturerange and to control soot. It may also be desirable if a viscosity indeximprover were capable of achieving (i) and (ii).

Unless otherwise indicated, each chemical or composition referred toherein should be interpreted as being a commercial grade material whichmay contain the isomers, by-products, derivatives, and other suchmaterials which are normally understood to be present in the commercialgrade. However, the amount of each chemical component is presentedexclusive of any solvent or diluent oil, which may be customarilypresent in the commercial material, unless otherwise indicated.

In one embodiment the present invention provides a lubricatingcomposition comprising an oil of lubricating viscosity and a compoundcomprising the reaction product of a polyolefin, an ethylenicallyunsaturated aromatic acylating agent (or carboxylic reactant), and anamine.

In one embodiment the present invention provides a lubricatingcomposition comprising an oil of lubricating viscosity and a compoundcomprising the reaction product of a polyolefin, an ethylenicallyunsaturated aromatic acylating agent (or carboxylic reactant), and anaromatic amine (typically wherein the aromatic amine is not aheterocycle).

In one embodiment the present invention provides a lubricatingcomposition comprising (i) an oil of lubricating viscosity, (ii) acompound comprising the reaction product of a polyolefin, anethylenically unsaturated aromatic acylating agent (or carboxylicreactant), and an amine, and (iii) an overbased metal-containingdetergent.

In one embodiment the lubricating composition disclosed herein has asulphated ash content of 0.3 wt % to 1.2 wt %, or 0.5 wt % to 1.1 wt %of the lubricating composition. The sulphated ash content may bedetermined by ASTM D-874.

The compound disclosed herein may be borated, or non-borated, typicallynon-borated.

In one embodiment the invention provides a lubricating compositionwherein the compound disclosed herein may be present at 0.1 wt % to 15wt %, or 1 wt % to 14 wt %, or 2 wt % to 12 wt %, or 4 wt % to 9 wt % ofthe lubricating composition. Typically the compound is present at anactives level of about 50 wt % of the ranges quoted. In other words, onan actives basis the compound may be present at 0.05 to 7.5 wt %, or 0.5wt % to 7 wt %, or 1 wt % to 6 wt %, or 2 wt % to 4.5 wt % of thelubricating composition.

In one embodiment the invention provides a lubricating compositioncomprising the compound disclosed herein and an alkylated diarylamine(such as an alkylated diphenylamine, or an alkylatedphenylnapthylamine). The alkylated diphenylamine may includedi-nonylated diphenyl amine, nonyl diphenyl amine, octyl diphenylamine,di-octylated diphenylamine, di-decylated diphenylamine, decyldiphenylamine and mixtures thereof. In one embodiment the diphenylaminemay include nonyl, diphenylamine, dinonyl diphenylamine, octyldiphenylamine, dioctyl diphenylamine, or mixtures thereof. In oneembodiment the diphenylamine may include nonyl, diphenylamine, ordinonyl diphenylamine. The alkylated diarylamine may include octyl,di-octyl, nonyl, di-nonyl, decyl or di-decyl phenylnapthylamines.

When present, the alkylated diarylamine may be present at 0.01 wt % to 5wt %, or 0.05 wt % to 3 wt %, or 0.1 wt % to 1 wt % of the lubricatingcomposition.

In one embodiment the invention provides a lubricating compositionwherein the compound as disclosed herein may be present at 2 wt % to 12wt % (or typically 4 wt % to 9 wt %) and the alkylated diphenylamine maybe present at 0.05 wt % to 3 wt % (or typically 0.1 wt % to 1 wt %) ofthe lubricating composition.

In one embodiment the invention provides a method of lubricating aninternal combustion engine comprising supplying to the internalcombustion engine a lubricating composition as disclosed herein.

In one embodiment the invention provides for the use of the compounddescribed herein in a lubricant as a dispersant or dispersant viscositymodifier.

In one embodiment the invention provides for the use of the compounddisclosed herein in a lubricant as a dispersant or dispersant viscositymodifier in an internal combustion engine lubricant. Typically thedispersant or dispersant viscosity modifier is useful to mitigate sootthickening in an engine lubricant.

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides a lubricating composition, a method forlubricating an engine as disclosed above, and a use of the compound asdisclosed above.

Polyolefin

The polyolefin may be a homopolymer or a copolymer. The polyolefin maybe derivable (or derived) from an olefin with 2 to 20, or 2 to 10, or 2to 4 carbon atoms. The polyolefin is known in the state of the art.

In one embodiment, the polyolefin may be a polybutene, typically apolyisobutylene. Typically the polyisobutylene has a number averagemolecular weight of 350 to 5000, or 550 to 3000 or 750 to 2500.Typically, when the reaction product of the invention is a homopolymer(such as polybutene) the homopolymer may be part of a dispersant.

When in the form of a copolymer, the polyolefin may be a copolymer ofbutene and isoprene, or an ethylene-α-olefin copolymer. In oneembodiment the polyolefin may be a copolymer of an ethylene andpropylene copolymer. Typically, when the reaction product of theinvention is a copolymer the copolymer may be a dispersant viscositymodifier.

The number average molecular weight of a copolymer derivable from abutene and isoprene copolymer, or an ethylene-α-olefin copolymer may be500 to 200,000, 5000 to 200,000, 5,000 to 100,000, or 5,000 to 75,000.

Ethylenically Unsaturated Aromatic Acylating Agent (or CarboxylicReactant)

The ethylenically unsaturated aromatic acylating agent (or carboxylicreactant) may include cis-cinnamic acid, trans-cinnamic acid,phenylpropiolic acid, phenyl maleic anhydride, or mixtures thereof, orderivatives thereof (such esters, partial esters, amides, or partialamides (typically esters, or partial esters)). In one embodiment theethylenically unsaturated aromatic acylating agent (or carboxylicreactant) may include cis-cinnamic acid, trans-cinnamic acid,phenylpropiolic acid, or mixtures thereof. In one embodiment theethylenically unsaturated aromatic acylating agent (or carboxylicreactant) may include trans-cinnamic acid, or mixtures of cis and transcinnamic acid.

In one embodiment the ethylenically unsaturated acylating agent may alsoinclude a derivative of cinnamic acid that may be represented by theformula:

wherein

X may be —O—, >NR″,

R′ and R″ may independently be hydrogen or a hydrocarbyl group(typically containing 1 to 50, or 1 to 20 carbon atoms, andR may independently be hydrogen, —OH, —OR, NR′R″, or hydrocarbyl, andany two R groups together with other atoms may form 5 or 6 memberedrings that may be saturated or unsaturated.

Examples of a derivative of cinnamic acid include3,4-(methylenedioxy)cinnamic acid, 3,4,5-trimethoxy-trans-cinnamic acid,4-(dimethylamine)cinnamic acid, sinapic acid, 2-hydroxycinnamic acid,3,4-dimethoxycinnamic acid, 3-hydroxy-4-methoxycinnamic acid,4-methoxycinnamic acid, α-methylcinnamic acid, caffeic acid, coumarin,trans-3-hydroxycinnamic acid, 4-hydroxy-3-phenyl-2(5H)-furanone,(E)-3-(naphthalene-2-yl)acrylic acid, trans-3-(4-methoxybenzoyl)acrylicacid, 3-indoleacrylic acid, 2,3-diphenyl-acrylic acid, or3-(1-naphthyl)acrylic acid.

Amine

The amine may be a monoamine or a polyamine. The amine may be a linearor branched, cyclic or acyclic amine, or combinations thereof. When theamine is cyclic, the amine may be either an aromatic amine or anon-aromatic amine.

In one embodiment the amine may be acyclic, typically an acyclicpolyamine. The polyamine may be an aliphatic polyamine such as anethylenepolyamine, a propylenepolyamine, a butylenepolyamine, ormixtures thereof. In one embodiment the polyamine may be anethylenepolyamine. In one embodiment the aliphatic polyamine may beselected from the group consisting of ethylenediamine,diethylenetriamine, triethylenetetramine, tetraethylenepentamine,pentaethylenehexamine, polyamine still bottoms, and mixtures thereof.

In one embodiment the amine may be an aromatic amine (typically whereinthe aromatic amine is not a heterocycle). The aromatic amine includesaniline, nitroaniline, aminocarbazole, 4-aminodiphenylamine (ADPA), andcoupling products (also referred to as coupled products) of ADPA. In oneembodiment the amine may be 4-aminodiphenylamine (ADPA), or couplingproducts of ADPA.

Counted products of ADPA may be represented by the formula (1):

wherein independently each variable,R¹ may be hydrogen or a C₁₋₅ alkyl group (typically hydrogen);R² may be hydrogen or a C₁₋₅ alkyl group (typically hydrogen);U may be an aliphatic, alicyclic or aromatic group, with the provisothat when U is aliphatic, the aliphatic group may be linear or branchedalkylene group containing 1 to 5, or 1 to 2 carbon atoms; andw may be 1 to 10, or 1 to 4, or 1 to 2 (typically 1).

In one embodiment the coupled ADPA of Formula (1) may be represented byFormula (1a):

wherein independently each variable,R¹ may be hydrogen or a C₁₋₅ alkyl group (typically hydrogen);R² may be hydrogen or a C₁₋₅ alkyl group (typically hydrogen);U may be an aliphatic, alicyclic or aromatic group, with the provisothat when U is aliphatic, the aliphatic group may be linear or branchedalkylene group containing 1 to 5, or 1 to 2 carbon atoms; andw may be 1 to 10, or 1 to 4, or Ito 2 (typically 1).

Alternatively, the compound of Formula (1a) may also be represented by:

wherein each variable U, R¹, and R² are the same as described above andw is 0 to 9 or 0 to 3 or 0 to 1 (typically 0).

In one embodiment the aromatic amine may have at least 3 or aromaticgroups. Examples of an amine having at least 3 aromatic groups may berepresented by any of the following Formulae (2) and/or (3):

A coupled aromatic amine can be made by the reaction of an aromaticamine with an aldehyde (such as formaldehyde). A person skilled in theart will appreciate that compounds of Formulae (2) and (3) may alsoreact with the aldehyde described below to form acridine derivatives.Acridine derivatives that may be formed include compounds represented byFormula (2a) or (3a) below. In addition to these compounds representingthese formulae, a person skilled in the art will also appreciate thatother acridine structures may be possible where the aldehyde reacts withother benzyl groups bridged with the >NH group.

Examples of acridine structures include those represented by Formulae(2a) and (3a):

Any or all of the N-bridged aromatic rings are capable of such furthercondensation and perhaps aromatisation. One other of many possiblestructures is shown in Formula (3b).

Examples of the coupled ADPA includebis[p-(p-aminoanilino)phenyl]-methane,2-(7-amino-acridin-2-ylmethyl)-N-4-{4-[4-(4-amino-phenylamino)-benzyl]-phenyl}-benzene-1,4-diamine,N⁴-{4-[4-(4-amino-phenylamino)-benzyl]-phenyl}-2-[4-(4-amino-phenylamino)-cyclohexa-1,5-dienylmethyl]-benzene-1,4-diamine,N-[4-(7-amino-acridin-2-ylmethyl)-phenyl]-benzene-1,4-diamine, ormixtures thereof.

The coupled ADPA may be prepared by a process comprising reacting thearomatic amine with an aldehyde. The aldehyde may be aliphatic,alicyclic or aromatic. The aliphatic aldehyde may be linear or branched.Examples of a suitable aromatic aldehyde include benzaldehyde oro-vanillin. Examples of an aliphatic aldehyde include formaldehyde (or areactive equivalent thereof such as formalin or paraformaldehyde),ethanal or propanal. Typically the aldehyde may be formaldehyde orbenzaldehyde.

The process may be carried out at a reaction temperature in the range of40° C. to 180° C., or 50° C. to 170° C.

The reaction may or may not be carried out in the presence of a solvent.Examples of a suitable solvent include diluent oil, benzene, t-butylbenzene, toluene, xylene, chlorobenzene, hexane, tetrahydrofuran, water,or mixtures thereof.

The reaction may be performed in either air or an inert atmosphere.Examples of suitable inert atmosphere include nitrogen or argon,typically nitrogen.

Alternatively, the coupled ADPA may also be prepared by the methodologydescribed in Berichte der Deutschen Chemischen Gesellschaft (1910), 43,728-39.

The compound of the invention may be obtained/obtainable by a processcomprising:

-   -   Step (1) reacting a polyolefin (typically a polybutene such as        polyisobutylene) with an ethylenically unsaturated aromatic        acylating agent (or carboxylic reactant); and    -   Step (2) reacting the product of step (1) with an amine.

The polybutene may be reacted with chlorine to provide a substancecapable of undergoing a Diels-Alder reaction with the ethylenicallyunsaturated acylating agent. Alternatively, the polybutene and/or theethylene alpha olefin may be reacted with the ethylenically unsaturatedacylating agent in the presence of a radical initiator.

The mole ratio of polyolefin to ethylenically unsaturated aromaticacylating agent (or carboxylic reactant) may range from 5:1 to 1:5, or3:1 to 1:3, or 2:1 to 1:2, or 1:1. When the mole ratio is about 1:1 theproduct of step (1) is typically mono-substituted.

Step (2) of the process reacts an amine with the product of step (1) byprocesses known to a person skilled in the art. The mole ratio of theamine to the product of step (1) may vary from 0.3:1 or 0.5:1 or 1:1 or2:1, to 3:1 or to 2:1, e.g., 0.5:1 to 2:1. In certain embodiments, therelative amounts may be expressed in terms of the ratio of nitrogenatoms to carbonyl groups, and typical N:CO ratios may include 0.5:1 to5:1. Typically the product of step (2) is in the form an amide.

When the polyolefin is a polyisobutylene, the ethylenically unsaturatedacylating agent is trans-cinnamic acid, and any amine disclosed hereinare reacted, the product formed may be represented by formulae:

wherein w may be 1 to 5, or 1 to 3 (depending on the mole ratio of theproduct of the amine to the product of step (1) or step (i));Q may be the residue of polybutene;Ph may be phenyl group derivable from trans-cinnamic acid;and Am may be the residue of the amine reacted.

The compound of the invention may be obtained/obtainable by a processcomprising (i) reacting a polyolefin copolymer (typically anethylene-α-olefin copolymer) with an ethylenically unsaturated aromaticacylating agent (or carboxylic reactant); and (ii) reacting the productof (i) with an amine.

The ethylenically unsaturated aromatic acylating agent (or carboxylicreactant) may be grafted onto the polyolefin copolymer (typically anethylene/propylene copolymer) in a number of ways. It may be graftedonto the polymer in solution or in molten form using a radicalinitiator. The free-radical induced grafting of ethylenicallyunsaturated carboxylic acid materials may also be conducted in solvents,such as hexane or mineral oil. It may be carried out at an elevatedtemperature in the range of 100° C. to 250° such as 120° C. to 190° C.or 150° C. to 180° C. If grafting is conducted in a solvent such as amineral lubricating oil solution, the solution may contain 1 wt % to 50wt %, or 5 wt % to 30 wt % based on the initial total oil solution, ofthe polyolefin copolymer, typically under an inert environment.

The free-radical initiators which may be used include peroxides,hydroperoxides, and azo compounds, typically those which have a boilingpoint greater than about 100° C. and which decompose thermally withinthe grafting temperature range to provide free radicals. Representativeof these free-radical initiators include azobisisobutyronitrile and2,5-dimethyl-hex-3-yne-2,5-bis-tertiary-butyl peroxide. The initiator istypically used in an amount of 0.005 wt % to 1 wt % based on the weightof the reaction mixture solution. The grafting is typically carried outin an inert atmosphere, such as under nitrogen blanketing. The resultingpolymer intermediate is characterized by having the aromatic acylatingfunctions within its structure.

In a melt process for forming a graft polymer, the ethylenicallyunsaturated aromatic acylating agent (or carboxylic reactant), with theoptional use of a radical initiator, is grafted onto molten rubber usingrubber masticating or shearing equipment. The temperature of the moltenmaterial in this process may be 70° C. to 250° C. Optionally, as a partof this process or separate from this process, mechanical shear andelevated temperatures can be used to reduce the molecular weight of thecopolymer to a value that will eventually provide the desired level ofshear stability for the lubricant application. In one embodiment, suchmastication can be done in a twin screw extruder properly configured toprovide high shear zones, capable of breaking down the polymer to thedesired molecular weight. Shear degradation can be done before or aftergrafting with the maleic anhydride. It can be done in the absence orpresence of oxygen. The shearing and grafting steps can be done in thesame extruder or in separate extruders, in any order.

In an alternative embodiment, the ethylenically unsaturated aromaticacylating agent (or carboxylic reactant), may be first condensed with anamine (as described herein) and the condensation product itself thengrafted onto the polymer backbone in analogous fashion to that describedabove.

The amount of the ethylenically unsaturated aromatic acylating agent (orcarboxylic reactant) on the polymer chain, and in particular the amountof grafted carboxylic acid on the chain is typically 1 wt % to 5 wt %based on the weight of the polyolefin backbone, and in an alternativeembodiments 1.5 wt % to 4 wt 5, or 1.5 wt % to 3.5 wt %. These numbersrepresent the amount of ethylenically unsaturated aromatic acylatingagent (or carboxylic reactant) monomer and may be adjusted to accountfor acid monomers having higher or lower molecular weights or greater orlesser amounts of acid functionality per molecule, as will be apparentto the person skilled in the art.

The product of step (i) may then be functionalised by the amine in step(2). This reaction step is similar to that described above forpolybutene.

The product of step (ii) may in some instances be a dispersant viscositymodifier (DVM).

Oils of Lubricating Viscosity

The lubricating composition comprises an oil of lubricating viscosity.Such oils include natural and synthetic oils, oil derived fromhydrocracking, hydrogenation, and hydrofinishing, unrefined, refined,re-refined oils or mixtures thereof. A more detailed description ofunrefined, refined and re-refined oils is provided in InternationalPublication WO2008/147704, paragraphs [0054] to [0056] and in thecorresponding paragraphs of US-2010-0197536. A more detailed descriptionof natural and synthetic lubricating oils is described in paragraphs[0058] to [0059] respectively of WO2008/147704. Synthetic oils may alsobe produced by Fischer-Tropsch reactions and typically may behydroisomerised Fischer-Tropsch hydrocarbons or waxes. In one embodimentoils may be prepared by a Fischer-Tropsch gas-to-liquid syntheticprocedure as well as other gas-to-liquid oils.

Oils of lubricating viscosity may also be defined as specified in April2008 version of “Appendix E—API Base Oil Interchangeability Guidelinesfor Passenger Car Motor Oils and Diesel Engine Oils”, section 1.3Sub-heading 1.3. “Base Stock Categories”. In one embodiment the oil oflubricating viscosity may be an API Group II or Group III oil.

The amount of the oil of lubricating viscosity present is typically thebalance remaining after subtracting from 100 wt % the sum of the amountof the compound of the invention and the other performance additives.

The lubricating composition may be in the form of a concentrate and/or afully formulated lubricant. If the lubricating composition of theinvention (comprising the additives disclosed herein) is in the form ofa concentrate which may be combined with additional oil to form, inwhole or in part, a finished lubricant), the ratio of the of theseadditives to the oil of lubricating viscosity and/or to diluent oilinclude the ranges of 1:99 to 99:1 by weight, or 80:20 to 10:90 byweight.

A lubricating composition may be prepared by adding the product of theprocess described herein to an oil of lubricating viscosity, optionallyin the presence of other performance additives (as described hereinbelow).

Other Performance Additives

The composition optionally comprises other performance additives. Theother performance additives include at least one of metal deactivators,viscosity modifiers, detergents, friction modifiers, antiwear agents,corrosion inhibitors, dispersants (other than the compound of theinvention), dispersant viscosity modifiers (other than the compound ofthe invention), extreme pressure agents, antioxidants, foam inhibitors,demulsifiers, pour point depressants, seal swelling agents and mixturesthereof. Typically, fully-formulated lubricating oil will contain one ormore of these performance additives.

In one embodiment the lubricating composition further includes otheradditives. In one embodiment the invention provides a lubricatingcomposition further comprising at least one of a dispersant (other thanthe compound of the invention), an antiwear agent, a dispersantviscosity modifier (other than the compound of the invention), afriction modifier, a viscosity modifier, an antioxidant, an overbaseddetergent, or mixtures thereof. In one embodiment the invention providesa lubricating composition further comprising at least one of apolyisobutylene succinimide dispersant, an antiwear agent, a dispersantviscosity modifier, a friction modifier, a viscosity modifier (typicallyan olefin copolymer such as an ethylene-propylene copolymer), anantioxidant (including phenolic and aminic antioxidants), an overbaseddetergent (including overbased sulphonates and phenates), or mixturesthereof.

The dispersant may be a succinimide dispersant, or mixtures thereof. Inone embodiment the dispersant may be present as a single dispersant. Inone embodiment the dispersant may be present as a mixture of two orthree different dispersants, wherein at least one may be a succinimidedispersant.

The succinimide dispersant may be derived from an aliphatic polyamine,or mixtures thereof. The aliphatic polyamine may be aliphatic polyaminesuch as an ethylenepolyamine, a propylenepolyamine, a butylenepolyamine,or mixtures thereof. In one embodiment the aliphatic polyamine may beethylenepolyamine. In one embodiment the aliphatic polyamine may beselected from the group consisting of ethylenediamine,diethylenetriamine, triethylenetetramine, tetraethylenepentamine,pentaethylenehexamine, polyamine still bottoms, and mixtures thereof.

The dispersant may be an N-substituted long chain alkenyl succinimide.An example of an N-substituted long chain alkenyl succinimide ispolyisobutylene succinimide. Typically the polyisobutylene from whichpolyisobutylene succinic anhydride is derived has a number averagemolecular weight of 350 to 5000, or 550 to 3000 or 750 to 2500.Succinimide dispersants and their preparation are disclosed, forinstance in U.S. Pat. Nos. 3,172,892, 3,219,666, 3,316,177, 3,340,281,3,351,552, 3,381,022, 3,433,744, 3,444,170, 3,467,668, 3,501,405,3,542,680, 3,576,743, 3,632,511, 4,234,435, Re 26,433, and 6,165,235,7,238,650 and EP Patent Application 0 355 895 A.

The dispersant may also be post-treated by conventional methods by areaction with any of a variety of agents. Among these are boroncompounds, urea, thiourea, dimercaptothiadiazoles, carbon disulphide,aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinicanhydrides, maleic anhydride, nitriles, epoxides, and phosphoruscompounds.

The dispersant may be present at 0.01 wt % to 20 wt %, or 0.1 wt % to 15wt %, or 0.1 wt % to 10 wt %, or 1 wt % to 6 wt %, or 1 to 3 wt % of thelubricating composition.

In one embodiment the lubricating composition of the invention furthercomprises a dispersant viscosity modifier. The dispersant viscositymodifier may be present at 0 wt % to 5 wt %, or 0 wt % to 4 wt %, or0.05 wt % to 2 wt %, or 0.2 wt % to 1.2 wt % of the lubricatingcomposition.

The dispersant viscosity modifier may include functionalisedpolyolefins, for example, ethylene-propylene copolymers that have beenfunctionalized with an acylating agent such as maleic anhydride and anamine; polymethacrylates functionalised with an amine, or styrene-maleicanhydride copolymers reacted with an amine. More detailed descriptionsof dispersant viscosity modifiers are disclosed in InternationalPublication WO2006/015130 or U.S. Pat. Nos. 4,863,623; 6,107,257;6,107,258; and 6,117,825. In one embodiment the dispersant viscositymodifier may include those described in U.S. Pat. No. 4,863,623 (seecolumn 2, line 15 to column 3, line 52) or in International PublicationWO2006/015130 (see page 2, paragraph [0008], and preparative examplesare described paragraphs [0065] to [0073]).

In one embodiment the invention provides a lubricating composition whichfurther includes a phosphorus-containing antiwear agent. Typically thephosphorus-containing antiwear agent may be a zincdialkyldithiophosphate, a phosphite, phosphate, phosphonate, ammoniumphosphate salt, or mixtures thereof. Zinc dialkyldithiophosphates areknown in the art. The antiwear agent may be present at 0 wt % to 3 wt %,or 0.1 wt % to 1.5 wt %, or 0.5 wt % to 0.9 wt % of the lubricatingcomposition.

In one embodiment the invention provides a lubricating compositionfurther comprising a molybdenum compound. The molybdenum compound may beselected from the group consisting of molybdenumdialkyldithiophosphates, molybdenum dithiocarbamates, amine salts ofmolybdenum compounds, and mixtures thereof. The molybdenum compound mayprovide the lubricating composition with 0 to 1000 ppm, or 5 to 1000ppm, or 10 to 750 ppm 5 ppm to 300 ppm, or 20 ppm to 250 ppm ofmolybdenum.

In one embodiment the invention provides a lubricating compositionfurther comprising an overbased metal-containing detergent. The metal ofthe metal-containing detergent may be zinc, sodium, calcium ormagnesium.

The overbased metal-containing detergent may be selected from the groupconsisting of non-sulphur containing phenates, sulphur containingphenates, sulphonates, salixarates, salicylates, and mixtures thereof.

The overbased metal-containing detergent may also include “hybrid”detergents formed with mixed surfactant systems including phenate and/orsulphonate components, e.g. phenate/salicylates, sulphonate/phenates,sulphonate/salicylates, sulphonates/phenates/salicylates, as described;for example, in U.S. Pat. Nos. 6,429,178; 6,429,179; 6,153,565; and6,281,179. Where, for example, a hybrid sulphonate/phenate detergent isemployed, the hybrid detergent would be considered equivalent to amountsof distinct phenate and sulphonate detergents introducing like amountsof phenate and sulphonate soaps, respectively.

Typically an overbased metal-containing detergent may be a zinc, sodium,calcium or magnesium salt of a phenate, sulphur containing phenate,sulphonate, salixarate or salicylate. Overbased salixarates, phenatesand salicylates typically have a total base number of 180 to 450 TBN.Overbased sulphonates typically have a total base number of 250 to 600,or 300 to 500. Overbased detergents are known in the art. In oneembodiment the sulphonate detergent may be a predominantly linearalkylbenzene sulphonate detergent having a metal ratio of at least 8 asis described in paragraphs [0026] to [0037] of US Patent Application2005065045 (and granted as U.S. Pat. No. 7,407,919). The predominantlylinear alkylbenzene sulphonate detergent may be particularly useful forassisting in improving fuel economy.

Typically the overbased metal-containing detergent may be a calcium ormagnesium overbased detergent.

Overbased detergents are known in the art. Overbased materials,otherwise referred to as overbased or superbased salts, are generallysingle phase, homogeneous Newtonian systems characterized by a metalcontent in excess of that which would be present for neutralizationaccording to the stoichiometry of the metal and the particular acidicorganic compound reacted with the metal. The overbased materials areprepared by reacting an acidic material (typically an inorganic acid orlower carboxylic acid, preferably carbon dioxide) with a mixturecomprising an acidic organic compound, a reaction medium comprising atleast one inert, organic solvent (mineral oil, naphtha, toluene, xylene,etc.) for said acidic organic material, a stoichiometric excess of ametal base, and a promoter such as a phenol or alcohol. The acidicorganic material will normally have a sufficient number of carbon atomsto provide a degree of solubility in oil. The amount of excess metal iscommonly expressed in terms of metal ratio. The term “metal ratio” isthe ratio of the total equivalents of the metal to the equivalents ofthe acidic organic compound. A neutral metal salt has a metal ratio ofone. A salt having 4.5 times as much metal as present in a normal saltwill have metal excess of 3.5 equivalents, or a ratio of 4.5. The termmetal ratio is also explained in standard textbook entitled “Chemistryand Technology of Lubricants”, Second Edition, Edited by R. M. Mortierand S. T. Orszulik, Copyright 1997. In one embodiment, the lubricantcomposition comprises at least one overbased detergent with a metalratio of at least 3, or at least 8, or at least 15.

The overbased detergent may be present at 0 wt % to 15 wt %, or 0.1 wt %to 10 wt %, or 0.2 wt % to 8 wt %, or 0.2 wt % to 3 wt %. For example,in a heavy duty diesel engine the detergent may be present at 2 wt % to3 wt % of the lubricating composition. Similarly, for example, in apassenger car engine the detergent may be present at 0.2 wt % to 1 wt %of the lubricating composition.

In one embodiment the lubricating composition includes an antioxidant,or mixtures thereof. The antioxidant may be present at 0 wt % to 15 wt%, or 0.1 wt % to 10 wt %, or 0.5 wt % to 5 wt %, or 0.5 wt % to 3 wt %of the lubricating composition.

Antioxidants include sulphurised olefins, alkylated diphenylamines (asdescribed previously), hindered phenols, molybdenum compounds (such asmolybdenum dithiocarbamates), or mixtures thereof.

The hindered phenol antioxidant often contains a secondary butyl and/ora tertiary butyl group as a sterically hindering group. The phenol groupmay be further substituted with a hydrocarbyl group (typically linear orbranched alkyl) and/or a bridging group linking to a second aromaticgroup. Examples of suitable hindered phenol antioxidants include2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol,4-ethyl-2,6-di-tert-butylphenol, 4-propyl-2,6-di-tert-butylphenol or4-butyl-2,6-di-tert-butylphenol, or 4-dodecyl-2,6-di-tert-butylphenol.In one embodiment the hindered phenol antioxidant may be an ester andmay include, e.g., Irganox™ L-135 from Ciba. A more detailed descriptionof suitable ester-containing hindered phenol antioxidant chemistry isfound in U.S. Pat. No. 6,559,105.

In one embodiment the friction modifier may be selected from the groupconsisting of long chain fatty acid derivatives of amines, long chainfatty esters, or derivatives of a long chain fatty epoxides; fattyimidazolines; amine salts of alkylphosphoric acids; fatty alkyltartrates; fatty alkyl tartrimides; and fatty alkyl tartramides. Thefriction modifier may be present at 0 wt % to 6 wt %, or 0.05 wt % to 4wt %, or 0.1 wt % to 2 wt % of the lubricating composition.

As used herein the term “fatty” or “fatty alkyl” means a carbon chainhaving 10 to 22 carbon atoms, typically a straight carbon chain.

Examples of suitable friction modifiers include long chain fatty acidderivatives of amines, fatty esters, or fatty epoxides; fattyimidazolines such as condensation products of carboxylic acids andpolyalkylene-polyamines; amine salts of alkylphosphoric acids; fattyalkyl tartrates; fatty alkyl tartrimides; or fatty alkyl tartramides.

Friction modifiers may also encompass materials such as sulphurisedfatty compounds and olefins, molybdenum dialkyldithiophosphates,molybdenum dithiocarbamates, sunflower oil or soybean oil monoester of apolyol and an aliphatic carboxylic acid.

In one embodiment the friction modifier may be a long chain fatty acidester. In another embodiment the long chain fatty acid ester may be amono-ester and in another embodiment the long chain fatty acid ester maybe a triglyceride.

Other performance additives such as corrosion inhibitors include thosedescribed in paragraphs 5 to 8 of WO2006/047486, octylamine octanoate,condensation products of dodecenyl succinic acid or anhydride and afatty acid such as oleic acid with a polyamine. In one embodiment thecorrosion inhibitors include the Synalox® corrosion inhibitor. TheSynalox® corrosion inhibitor may be a homopolymer or copolymer ofpropylene oxide. The Synalox® corrosion inhibitor is described in moredetail in a product brochure with Form No. 118-01453-0702 AMS, publishedby The Dow Chemical Company. The product brochure is entitled “SYNALOXLubricants, High-Performance Polyglycols for Demanding Applications.”

Metal deactivators including derivatives of benzotriazoles (typicallytolyltriazole), dimercaptothiadiazole derivatives, 1,2,4-triazoles,benzimidazoles, 2-alkyldithiobenzimidazoles, or2-alkyldithiobenzothiazoles; foam inhibitors including copolymers ofethyl acrylate and 2-ethylhexylacrylate and optionally vinyl acetate;demulsifiers including trialkyl phosphates, polyethylene glycols,polyethylene oxides, polypropylene oxides and (ethylene oxide-propyleneoxide) polymers; pour point depressants including esters of maleicanhydride-styrene, polymethacrylates, polyacrylates or polyacrylamidesmay be useful. Foam inhibitors that may be useful in the compositions ofthe invention include silicones such as polysiloxanes, copolymers ofethyl acrylate and 2-ethylhexylacrylate and optionally vinyl acetate;demulsifiers including trialkyl phosphates, polyethylene glycols,polyethylene oxides, polypropylene oxides and (ethylene oxide-propyleneoxide) polymers.

Pour point depressants that may be useful in the compositions of theinvention include polyalphaolefins, esters of maleic anhydride-styrene,poly(meth)acrylates, polyacrylates or polyacrylamides.

In different embodiments the lubricating composition may have acomposition as described in the following table:

Embodiments (wt %) Additive A B C Compound of the Invention 0.1 to 15 1to 14 4 to 9 Dispersant 0 to 12 0 to 8 0.5 to 6 Dispersant ViscosityModifier 0 to 5 0 to 4 0.05 to 2 Overbased Detergent 0 to 15 0.1 to 100.2 to 8 Antioxidant 0 to 13 0.1 to 10 0.5 to 5 Antiwear Agent 0 to 150.1 to 10 0.3 to 5 Friction Modifier 0 to 6 0.05 to 4 0.1 to 2 ViscosityModifier 0 to 10 0.5 to 8 1 to 6 Any Other Performance Additive 0 to 100 to 8 0 to 6 Oil of Lubricating Viscosity Balance to Balance to Balanceto 100% 100% 100%

INDUSTRIAL APPLICATION

The lubricating composition may be utilised in an internal combustionengine. The engine components may have a surface of steel or aluminium(typically a surface of steel).

An aluminium surface may be derived from an aluminium alloy that may bea eutectic or a hyper-eutectic aluminium alloy (such as those derivedfrom aluminium silicates, aluminium oxides, or other ceramic materials).The aluminium surface may be present on a cylinder bore, cylinder block,or piston ring having an aluminium alloy, or aluminium composite.

The internal combustion engine may or may not have an Exhaust GasRecirculation system. The internal combustion engine may be fitted withan emission control system or a turbocharger. Examples of the emissioncontrol system include diesel particulate filters (DPF), or systemsemploying selective catalytic reduction (SCR).

In one embodiment the internal combustion engine may be a diesel fuelledengine (typically a heavy duty diesel engine), a gasoline fuelledengine, a natural gas fuelled engine or a mixed gasoline/alcohol fuelledengine. In one embodiment the internal combustion engine may be a dieselfuelled engine and in another embodiment a gasoline fuelled engine. Inone embodiment the internal combustion engine may be a heavy duty dieselengine. In one embodiment the internal combustion engine may be a heavyduty diesel engine equipped with exhaust gas recirculation.

The internal combustion engine may be a 2-stroke or 4-stroke engine.Suitable internal combustion engines include marine diesel engines,aviation piston engines, low-load diesel engines, and automobile andtruck engines.

The lubricant composition for an internal combustion engine may besuitable for any engine lubricant irrespective of the sulphur,phosphorus or sulphated ash (ASTM D-874) content. The sulphur content ofthe engine oil lubricant may be 1 wt % or less, or 0.8 wt % or less, or0.5 wt % or less, or 0.3 wt % or less. In one embodiment the sulphurcontent may be in the range of 0.001 wt % to 0.5 wt %, or 0.01 wt % to0.3 wt %. The phosphorus content may be 0.2 wt % or less, or 0.12 wt %or less, or 0.1 wt % or less, or 0.085 wt % or less, or 0.08 wt % orless, or even 0.06 wt % or less, 0.055 wt % or less, or 0.05 wt % orless. In one embodiment the phosphorus content may be 0.4 wt % to 0.12wt %. In one embodiment the phosphorus content may be 100 ppm to 1000ppm, or 200 ppm to 600 ppm. The total sulphated ash content may be 0.3wt % to 1.2 wt %, or 0.5 wt % to 1.1 wt % of the lubricatingcomposition. In one embodiment the sulphated ash content may be 0.5 wt %to 1.1 wt % of the lubricating composition.

In one embodiment the lubricating composition may be an engine oil,wherein the lubricating composition may be characterised as having atleast one of (i) a sulphur content of 0.5 wt % or less, (ii) aphosphorus content of 0.12 wt % or less, and (iii) a sulphated ashcontent of 0.5 wt % to 1.1 wt % of the lubricating composition.

The following examples provide illustrations of the invention. Theseexamples are non-exhaustive and are not intended to limit the scope ofthe invention.

EXAMPLES Preparative Example 1 (EX1)

A 5 L 5 neck flask is charged with 1326.8 g of polyisobutylene(vinylidene content of 5-8 mol %, and number average molecular weight ofabout 2050) and 1044 g of hexane. A thermocouple, water condenser andtwo subsurface gas inlet tubes are connected to the flask. Prior to thegas inlet, two sinter gas filters, air trap and flow meter areconnected. Prior to the flow meter an air trap is connected. After thecondenser, a dry-ice tap, air trap, o-toluidine trap, water trap (500mL) and caustic trap are connected. The contents of the flask arestirred for 2 hours. The flask is then heated to 65° C. and 58 g ofchlorine is added over a period of 4 hours. The reaction is blown withnitrogen gas for 30 minutes, before cooling to ambient temperature. Theflask is then heated to 130° C. over 4 hours to remove hexane undervacuum. The reaction yields 1293.5 g of product.

Preparative Example 2 (EX2)

979.4 g of the product of EX1 and 982.4 g of dodecane are charged into a500 ml flask. The flask has a Friedrichs condenser attached and Tygon™tubing from the condenser outlet to a caustic trap. The thermocouple isplaced in a pocket to prevent corrosion and a PTFE stirrer is used. Thecontents of the flask are stirred for 30 minutes at 50° C.Trans-cinnamic acid (146.5 g) is then added at room temperature via apowder funnel. The resulting mixture is stirred (250 rpm) and heated to90° C. under nitrogen. The mixture is then heated to 180° C. over 1 hourand held at 180° C. for 18 hours. The reaction is then vacuum strippedover 7 hours while increasing the temperature from 150° C. to 200° C.,before cooling to ambient temperature.

Preparative Example 3 (EX3)

292.7 g of the product of EX1 and 250 g of dodecane are charged into a 1L flask. The flask has a Friedrichs condenser attached and Tygon™ tubingfrom the condenser outlet to a caustic trap. The thermocouple is placedin a pocket to prevent corrosion and a PTFE stirrer is used. Thecontents of the flask are stirred for 30 minutes at 50° C. beforecooling to ambient temperature. 32.5 g of phenylpropiolic acid is addedin one portion. The resulting mixture is stirred (250 rpm) and heated to90° C. under nitrogen. The mixture is then heated to 180° C. over 1.5hour and held at 180° C. for 18 hours. The reaction is then vacuumstripped over 10 hours while increasing the temperature from 150° C. to200° C., before cooling to ambient temperature.

Preparative Example 4 (EX4)

230.3 g of the product of EX2 and 235.4 g of diluent oil are placed in a1 L flask and heated to 110° C. under a nitrogen atmosphere. Thecontents of the flask are stirred at 200 rpm. 6.6 g oftriethylenetetramine is added dropwise (subsurface) over a period of 10minutes. The temperature is increased to 155° C. over a period of 15minutes. The flask is held at 155° C. for 4 hours.

Preparative Example 5 (EX5)

254.3 g of the product of EX2, 275.2 g of diluent oil are placed in a 1L flask and heated to 110° C. under a nitrogen atmosphere. The contentsof the flask are stirred at 200 rpm. 21.7 g of 4-aminodiphenylamine isadded portionwise via a powder funnel over 5 minutes. The temperature isincreased to 155° C. and held for 12 hours and then raised to at 180° C.and held for 5 hours. The flask is cooled to 100° C. and filtered over aperiod of 1 hour. The flask is then cooled to ambient temperature.

Preparative Example 6 (EX6)

A 2-L four neck flask equipped with an overhead stirrer, thermowell,subsurface nitrogen feed topped with addition funnel, and condenser ischarged with 8000 Mn olefin copolymer (derived from ethylene andpropylene) (500.0 g), trans-cinnamic acid (10.0 g) and t-butyl benzene(1000 mL) and heated to 150° C. A solution of t-butyl peroxide (4.9 g)in t-butyl benzene (100 mL) is charged to the addition funnel and addedto the flask subsurface over 60 min. The reaction is stirred at 150° C.for an additional 5 hours, then vacuum stripped at reduced pressure. Aviscous product is obtained (510.0 g).

Preparative Example 7 (EX7)

A 3-L, 4-neck flask equipped with an overhead stirrer, thermowell,subsurface inlet with nitrogen line, and Dean-Stark trap with condenseris charged with the product of EX6 (510.0 g) and diluent oil (1107.3 g)and heated to 110° C. Dimethylaminopropylamine (6.8 g) is added in oneportion, subsurface. The temperature is then raised to 160° C. and heldat that temperature for 10 hours. The resultant product is a darkviscous oil (1628.4 g).

A series of SAE 15W-40 heavy duty diesel engine lubricants (IVL1 toIVL3) are prepared containing antioxidants (mixture hindered phenols andalkylated diphenylamines), 1.09 wt % of zinc dialkyldithiophosphate, amixture of detergents (including calcium sulphonate and calciumphenate), 0.2 wt % of 2-tert-nonyldithio-5-mercapto-1,3,4-thiadiazoleand further containing 2 wt % of a dispersant viscosity modifier asdescribed in International Publication WO2006/015130 (see preparativeexamples described in paragraphs [0065] to [0073]). IVL1, IVL2 and IVL3contain 4.1 wt % of EX4, EX5 and EX7 respectively.

Comparative Example 1 (CE1) is a SAE 15W-40 engine lubricant similar toIVL1, except it replaces the reaction product of the present inventionwith 4.1 wt % of a succinimide dispersant.

IVL1 to IVL2 and CE1 are evaluated for performance for soot dispersancy.The lubricants are stressed by addition of 1 vol % of a 17.4 M mixtureof sulphuric and nitric acid (10:1) (amount of acid calculated to reduceTBN by 11). The acid stressed samples are top treated with 6 wt % carbonblack (soot model) and 5 wt % diesel fuel. The lubricant mixture is thehomogenised in a tissumizer to make a slurry. The slurry is thensonicated to completely disperse the carbon black. The dispersed sampleis stored at 90° C. for 7 days while blowing 0.5 cc min⁻¹ of 0.27%nitrous oxide in air through the sample. 25 microliter aliquots ofsample are blotted onto chromatography paper once daily. After curingthe filter paper for 2 hours at 90° C., the ratio of the diameter of theinternal carbon black containing spot to the external oil spot (×100) ismeasured, averaged over 7 days and reported in the table as soot ratio.Higher soot ratio indicates improved soot dispersion. The resultsobtained are as follows:

CE1 IVL1 IVL2 IVL3 Soot Ratio 43 70 72 N.M. Footnote: N.M. indicates notmeasured.

The results indicate that high soot ratio correlates to better sootdispersion.

It is known that some of the materials described above may interact inthe final formulation, so that the components of the final formulationmay be different from those that are initially added. The productsformed thereby, including the products formed upon employing lubricantcomposition of the present invention in its intended use, may not besusceptible of easy description. Nevertheless, all such modificationsand reaction products are included within the scope of the presentinvention; the present invention encompasses lubricant compositionprepared by admixing the components described above.

Each of the documents referred to above is incorporated herein byreference. Except in the Examples, or where otherwise explicitlyindicated, all numerical quantities in this description specifyingamounts of materials, reaction conditions, molecular weights, number ofcarbon atoms, and the like, are to be understood as modified by the word“about.” It is to be understood that the upper and lower amount, range,and ratio limits set forth herein may be independently combined.Similarly, the ranges and amounts for each element of the invention maybe used together with ranges or amounts for any of the other elements.

As used herein, the term “hydrocarbyl substituent” or “hydrocarbylgroup” is used in its ordinary sense, which is well-known to thoseskilled in the art. Specifically, it refers to a group having a carbonatom directly attached to the remainder of the molecule and havingpredominantly hydrocarbon character. Examples of hydrocarbyl groupsinclude: hydrocarbon substituents, including aliphatic, alicyclic, andaromatic substituents; substituted hydrocarbon substituents, that is,substituents containing non-hydrocarbon groups which, in the context ofthis invention, do not alter the predominantly hydrocarbon nature of thesubstituent; and hetero substituents, that is, substituents whichsimilarly have a predominantly hydrocarbon character but contain otherthan carbon in a ring or chain. A more detailed definition of the term“hydrocarbyl substituent” or “hydrocarbyl group” is described inparagraphs [0118] to [0119] of International Publication WO2008147704and paragraphs [0137] to [0141] of published application US2010-0197536.

While the invention has been explained in relation to its preferredembodiments, it is to be understood that various modifications thereofwill become apparent to those skilled in the art upon reading thespecification. Therefore, it is to be understood that the inventiondisclosed herein is intended to cover such modifications as fall withinthe scope of the appended claims.

1.-20. (canceled)
 21. A lubricating composition comprising an oil oflubricating viscosity and 0.1 wt % to 15 wt % of a compound comprisingthe reaction product of a polyolefin, an ethylenically unsaturatedaromatic acylating agent, and an amine, wherein the amine is an acyclicpolyamine, wherein the polyolefin is a polybutene, and wherein thelubricating composition has a sulphated ash content of 0.3 wt % to 1.2wt % of the lubricating composition.
 22. The lubricating composition ofclaim 21, wherein the amine is an ethylenepolyamine.
 23. The lubricatingcomposition of claim 22, wherein the ethylenepolyamine is selected fromthe group consisting of ethylenediamine, diethylenetriamine,triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine,polyamine still bottoms, and mixtures thereof.
 24. The lubricatingcomposition of claim 21, wherein the polyolefin is derivable from anolefin with 2 to 4 carbon atoms.
 25. The lubricating composition ofclaim 21, wherein the polyolefin is a polyisobutylene.
 26. Thelubricating composition of claim 21, wherein the polyolefin is acopolymer, wherein the polyolefin is a butene and isoprene copolymer, oran ethylene-α-olefin copolymer.
 27. The lubricating composition of claim26, wherein the ethylene-α-olefin copolymer is an ethylene-propylenecopolymer.
 28. The lubricating composition of claim 21, wherein theethylenically unsaturated aromatic acylating agent is cis-cinnamic acid,trans-cinnamic acid, or mixtures thereof.
 29. The lubricatingcomposition of claim 21, wherein the compound is obtained by a processcomprising: (1) reacting the polyolefin with the ethylenicallyunsaturated aromatic acylating agent; and (2) reacting the product ofstep (1) with the amine.
 30. The lubricating composition of claim 21,wherein the compound is non-borated.
 31. The lubricating composition ofclaim 21, wherein the compound is present at 2 wt % to 12 wt %, of thelubricating composition.
 32. The lubricating composition of claim 21,wherein the lubricating composition has a sulphated ash content of 0.5wt % to 1.1 wt % of the lubricating composition.
 33. The lubricatingcomposition of claim 21 further comprising an overbased metal-containingdetergent, wherein the overbased metal-containing detergent is selectedfrom the group consisting of non-sulphur containing phenates, sulphurcontaining phenates, sulphonates, salixarates, salicylates, and mixturesthereof.
 34. A method of lubricating an internal combustion enginecomprising supplying to the internal combustion engine a lubricatingcomposition comprising the lubricating composition of claim
 21. 35. Alubricating composition comprising an oil of lubricating viscosity and0.1 wt % to 15 wt % of a compound comprising the reaction product of apolyolefin, an ethylenically unsaturated aromatic acylating agent (orcarboxylic reactant), and an amine, wherein the aromatic amine isselected from the group consisting of aniline, nitroaniline,aminocarbazole, 4-aminodiphenylamine (ADPA), and coupling products ofADPA.
 36. The lubricating composition of claim 35, wherein the aromaticamine is 4-aminodiphenylamine or coupling products of4-aminodiphenylamine.
 37. The lubricating composition of claim 34,wherein the polyolefin is a polyisobutylene.
 38. The lubricatingcomposition of claim 34, wherein the polyolefin is a copolymer, whereinthe polyolefin is a butene and isoprene copolymer, or anethylene-α-olefin copolymer.
 39. The lubricating composition of claim34, wherein the lubricating composition has a sulphated ash content of0.5 wt % to 1.1 wt % of the lubricating composition.
 40. A method oflubricating an internal combustion engine comprising supplying to theinternal combustion engine a lubricating composition comprising thelubricating composition of claim 34.